analysis of aluminium oxide and silicon carbide ceramic materials

8/11/2019 Analysis of Aluminium Oxide and Silicon Carbide Ceramic Materials

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J O U R N A L

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A N A L Y TI CA L A T O M I C S P E C T R O M E T R Y , S E P T E M B E R 1994, V O L .

9 1063

Analysis of Aluminium Oxide and Silicon Carbide Ceramic Materials

by Inductively Coupled Plasma Mass Spectrometry

Invited Lecture

J. A. C. Broekaert

Universitat Dortmund, Fachbereich Chemie, 0-44227 Dortmund, Germany

R. Brandt

Max-Planck-lnstitut fur Metallforschung, Stuttgart, Laboratorium fur Reinststoffanalytik, Postfach 722652,

0-44073 Dortmund, Germany

F. Leis

C.

Pilger

and

D. Pollmann

lnstitut fur Spektrochemie und angewandte Spektroskopie, Postfach 707352,D-44073, Germany

P. Tschopel and G. Tolgt

Max-Planck-lnstitut fur Metallforschung, Stuttgart, Laboratorium fur Reinststoffanalytik, Postfach 122652,

0-44073 Dortmund, Germany

The use of inductively coupled plasma mass spectrometry (ICP-MS) for trace element determinations in

A1203 and Sic powders as well as in compact Sic ceramics, subsequent to grinding to a particle size of


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ANALYTICAL A TOMIC SPECTROM ETRY, SEPTEMBER 1994, VOL. 9

Elemental, Winsford, UK) , the instrumental d ata and working

parameters for which are listed in Table 1. The analytical

parameters used were as proposed for the instrument by the

manu facturer. For th e direct analyses of the samples subsequent

to dissolution, pneumatic nebulization with a concentric glass

nebulizer (Meinhard Associates, Santa Ana, CA, USA) and

also with a Babington-type nebulizer (V-groove nebulizer,

Fisons Instruments, VG Elemental) positioned in a laboratory -

made cooled spray ch am ber 7 was used. In the on-line matrix

removal using complexation of the trace elements, adsorption

of the hexamethylenedithiocarbonate (H M D C ) complexes on

an RP18 column, solid-phase extraction and high-pressure

nebulization of the effluent were applied. A high-pressure

nebulization system (Fa. Knauer, Berlin, Germany), as devel-

oped by Berndt, was used in conjunction with desolvation,

including both water and a Peltier cooling.'

A combined knocking-grinding machine with a pestle as

well as

a

mor tar m ade of high-purity S i c (Elektroschmelzwerk,

Kempten) was used for grinding the compact S i c granulate

material. The mortar vessel was held in a steel enclosure

(Fig. 1). With this device it was found th at S i c granules w ith

grains of between 1 and 20 mm side lengths can be pulverized.

Below this grain size the grinding action of the machine was

not effective, as it seem ed that a certain size is required for the

pressure to w ork o n the granules. Below this size S i c pieces

were found not to be split.

Samp les and Reagents

Th e A1,0, powd ers analysed included AKP-20 (mean particle

size 0.57 pm, as ind icated by the m anufacturer, Sum itomo,

Japan) and AKP-30 [mean particle size measured by auto-

mated electron p robe microanalysis (EP MA ) 0.35 and 0.43 pm,

as indicated by the manufacturer, Sumitorno] as well as ME/03

(mean particle size measured by auto ma ted EP M A 0.35 pm).

The ME/03 is a powder which has been characterized

previously in a round-robin organized by the Arbeitskreis:

Refraktarwerkstoffe in the Chem iker Ausschul3 der Gesellschaft

Deutscher M etallhiitten- un d Bergleute (G DM B). The particle

size distribution of the powders was determined by both

autom ated EP M A (for a description of the m ethod, see ref. 9)

Table

1

Plus ICP-MS instrument

Instrumental and working parameters for the PQ2 Turbo

~~

Generator

Nebulizers

V-groove nebulizer

Concentric glass nebulizer

Spray chamber

Peristaltic pump

Interface

Sampler

Skimmer

Power

Gas flows

Outer

Intermediate

Aerosol carrier

Sample uptake rate

Sampling depth

Vacuum

1st stage

2nd stage

Mass spectrometer

Mass range

Dwell time

Detector

Henry, 2.0 kW, 27.12 MHz

Meinhard Associates

Scott-type made of quartz

Gilson Minipuls 3

Ni, aperture 1.0 mm

Ni, aperture 0.7 mm

1.35kW forward

10-15 W reflected

14lmin-'

0.9-1.5 min-'

0.9- 1.1 min 3 bar*)

0.75-1.1 ml min-'

10-12 mm

2.0-3.0 mbar

-=1 x mbar

2.0-3.0 x mbar

10-141 u for A1,0,, 5-239 u

for Sic

Dual mode, 640

ps,

pulse

counting mode, 320

ps

Analogue-pulse counting

'L

ortar

Rotating

vibrator

i

teel ho l de r

Fig.

1

Grinding device for compact Sic

and by laser stray radiation measurements (laser particle sizer,

Analysette 22- Fritsch, Idar-Ob erstein, Ge rm any ). Reasonable

agreement between the results was obtained, considering that

deviations possibly can arise from differences in the ultrasonic

treatment of the suspension being measured and artifacts from

the nuclepore filter loading encountered in the case of

EPM A (Fig. 2).

The S i c samples analysed were A10 (mean particle size

xl pm, as indicated by the manufacturer, H.C. Starck,

Gos lar, Germany) an d S-933 (Elektroschmelzwerk, Kem pten,

Germany) in the form of a powder (mean part ic le s ize ~ 0 . 8m,

as indicated by the manufacturer) and granules (grain size

-10

mm).

The HC l and the

H2S0,

used for the sam ple decomposition

were purified by sub-boiling distillation. All dilutions were

20

100

80

40

20

0

b) 0.1 oF o 2.0

/

20

10

B

0

0 5 1

5 10

D

a

m

ete

r/pm

Fig. 2 Particle size distribution obtained for the A1,0, powder

AKP-30 (Sumitomo, Japan) by:

a)

EPMA (mean diameter= 0.35 pm);

and b) aser light scattering (mean diameter=0.59 pm)

1bar= 1 x lo5 Pa.

View Article Online
http://dx.doi.org/10.1039/ja9940901063


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J O U R N A L OF ANALYTICAL AT OM IC SPECTRO METRY , SEPTEMBE R 1994, VOL. 9

made with H 2 0 doubly distilled in qu artz equipment. The H F

used (Merck, Darm stadt, Germany) was of Suprap ur quality.

For the preparation of the standard solutions the respective

Titrisol stock solutions (Merck) were used. Sample decompo-

sitions were performed at high temperature and pressure in

closed poly( tetrafluoroethylene) (P T F E ) vessels (Berghof DAB

111, Tubing en, Ger ma ny) . In the m atrix removal studies,

HMDC (Merck) and C,, RP18 columns (Fa. Knauer) were

used.

Results

and

Discussion

Analysis

ofA1203

Powders

After initial tests with an AlCl, solution, it was found th at the

analyte solution for ICP-MS investigations should not contain

more than ~ 2 0 0g ml of Al, which corresponds to a concen-

tration of 400 pg ml-' of A1,0,. Indeed, at higher concen-

trations high ablation of the sampler was observed and also a

glassy deposit was soon formed on the skimmer. Both lead to

clogging as well as to a deterioration of the short-term

precision, expressed by the relative stan dard deviations (RSDs)

and long-term drifts.

15

A

t

0 50

100

150

200 250

Time/min

Fig .3 Long-term stability in ICP-MS analyses of A1203 after acid

decomposition: A, 24Mg;B, 66Zn;C, '39La; D,139La:'I5In and E, 24Mg:

45Sc. Sample solutions: 10ng ml-' of

B,

Na, Mg, Ti, V, Cr, Mn, Co,

Ni,

Zn, Ga, Zr, Ba, La and Ce;

400

pg ml- of A1203,

10

ng ml-' In

and 50 ng ml-' of Sc in 0.04 moll- HC1-0.0064 moll- ' H 2 S 0 4 .

ICP-MS:

PQ2

Turbo Plus with quartz spray-chamber

(10

C)

(measurement conditions as in Table 1 . Measurement cycle: pre-flow,

90 s; measurement time, 5

x 60

s; rinsing with acid solution,

2.5

min

1065

At a sample concentration of 4 0 0 p g m l - ' of A120,, the

RSD s were 2-5% for impurity concen trations of 10 ng ml -'

a n d in a 0.0 4m o 11 -1 H C1 a nd 6 . 4 ~op3m o l l - ' H 2 S 0 4

solution, which are the concentrations of acid present after

acid decomposition of the samples. However, when adding

10

ng ml -' of In an d 50 ng ml -' of Sc as internal stand ards ,

the short-term precision for all elements investigated (B, Na,

Mg, Ti, V, Cr, Mn, Co, Ni, Zn, Ga, Zr, Ba, La and Ce)

becomes

of

the orde r of 1-2% an d drifts [with an intermediate

washing stage of 2.5 min after each sam ple (measurement cycle:

pre-flow 90 s, integration 5 x 60

s)]

after an initial period are

below 5% over a period of 4 h (Fig. 3).

For dissolution of the Al,O, powders treatment w ith HC1

and H,SO, at 225C according to the following procedure

was found to be optimum. A 1+0.001 g sample of A120,

powder was transferred into a 150 ml PT FE vessel (Fa.

Berghof) and 10ml of sub-boiled HCl plus 1 ml of sub-boiled

H,SO, and 5m l of H 2 0 were also added. The mixture was

allowed to react for 6 h at 225 C in the closed vessel. The

resulting solution had been diluted 1

+

2500. Four solutions

with matched acid concentrations and analyte concentrations

of 0.4, 4, 40 and 400 ng ml -' and containing 5 ng ml -l of Rh

as an internal standard were used for calibration purposes.

The rinsing solution used contained 4m l

of

sub-boiled HCl

and 0.4 ml

of

sub-boiled

H , S 0 4

in 1 1 of H,O.

For analyte concen trations of 400 pg m l-' of A1203 , the

detection limits obtained for ICP-MS (based on the 3s cri-

terion), with a non-cooled spray chamber and considering the

blank limitations of all reagents used, are listed in Table2.

They range from 0.1 to

4

pg g- ' and a re higher for the low

mass elements. However, severe blanks (N a) or sp ectral inter-

ferences (Ca, Fe and Zn) are seen to occur. In the case

of

the

instrument used, no systematic differences could be noticed

when comparing the detection limits obtained in the scanning

mode with those of the peak jumping mode for a dwell time

of 640ps per channel and 25 scan cycles. Furthermore, the

increased values found for a number of elements were clearly

due to spectral interferences by oxygen, chlorine or sulfur

containing cluster ions of argon (see Table

3).

Under the

conditions originally used, the detection limits with ICP-MS

for a number of elements with respect to the solid samples

were even lower than with ICP-AES, however, only for

elements with a mass below 60. At higher m asses this situation

changes, as, with IC P-AE S, it is no longer possible to determine

elements of interest in the concentration range required for the

analysis of advanced ceramics.

Table 2 Detection limits cL)

(3s

concept) of ICP-MS and ICP-AES for the analysis of A1203. Values in parentheses are for analyte solutions in

distilled H20. Other values based on four replicates (ICP-MS)

or

12 replicates (ICP-AES)

of

the decomposition with all acids

ICP-MS*

Scanning mode,

c,/ng ml

-

1.0

(0.25)

6.5 (0.4)

2.0 (1.9)

32 (6.4)

0.8 (0.4)

0.3 (0.1)

36 (4.3)

0.3 (0.07)

2.0 (0.4)

0.6 (1.4)

0.06 (0.03)

0.05 (0.04)

(0.01)

(0.02)

0.01 (0.01)

0.01)

Peak jumping

c,/ng ml-'

1.3 (0.1)

8.3 (1.3)

1.4 (1.4)

30 (3.8)

1.4 (0.1)

0.3 (0.06)

35 (2.6)

0.08

(0.06)

0.5

(0.07)

0.07 (0.07)

1.8

(0.2)

0.8 (1.1)

0.13

(0.07)

0.16 (0.16)

0.06 (0.05)

0.07 (0.05)

CLIPg g

-

3.2

18.0

3.5

75

3.5

0.75

0.75

1.2

0.18

4.5

1.5

0.32

0.32

0.15

0.17

87

Actual?

c,,lClg

g

0.6

1.1

0.7

1.2

0.04

0.024

0.08

0.04

0.8

0.008

0.23

0.002

0.008

0.008

ICP-AES:

C J P g

3

-

0.6

0.03

0.05

0.3

0.8

2.1

0.9

~~~~~~~ ~ ~

*

Sample dilution 1 +2500; PQ2 Turbo Plus.

7 Values obtained after cooling the quartz spray chamber down to

10

C.

$

From

ref.

3.

Sample

dilution

+50; 2 kW ICP, 0.9 m Czerny-Turner monochromator.

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J O U R N A L OF ANALYT1CA.L ATOM IC SPECTROM ETRY, SEPTEM BER 1994, VOL. 9

Table 3

with HCl-H2S04 in a PTFE vessel

Spectral interferences in ICP-MS for Alz03. Decomposition

Analyte

44Ca

47Ti

48Ti

51v

Cr

53Cr

Mn

56Fe

Fe

60Ni

64Zn

66Zn

71Ga

Interferen

12~160160, 2 7 ~ 1 1 6 0 ~

3 3 ~ 1 4 ~

3 2 ~ 1 6 0

35CPO

3 7 ~ 1 1 6 0

4 0 ~ ~ 1 6 0

35C1160H, 0Ar12C, 6Ar160, 6 S 1 6 0

40Ar'4NH

40Ar160H

Cones

3 2 ~ 1 6 0 1 6 0

34~160160,

3 2 ~ 3 4 s

36Ar35C1

In the case of the AK P-3 0 powder, results in the 0.1-2 pg g-'

range were obtained for B, Ti, Cr, Mn, Ni,

Cu,

Zr, Ba, La and

Ce (Table 4). The results obtained in the peak jump ing mode

agreed well with those of the scanning mode. Even with the

semiquantitative programe, the results deviated by less than a

factor of two w ith only a few exceptions. In the case

of

Fe and

Ca, however, severe deviations were obtained, which could

relate more to interference problems, as these are known

already from the early literature o n IC P- M S (see for example,

ref. lo), than to blank limitations. The accuracy of the IC P-M S

results obtained was evaluated by performing analyses of the

ME/03 powder, which has also been analysed extensively by

other techniques (Table 5 ) . Excepted for Fe, reasonable agree-

Table 4 Results for analysis of Al,03 powder (AKP-30) by ICP-MS.

All concentrations are in

pg

g- he standard deviations from four

replicate analyses; final dilution, 1

+

2500; and internal standard, Rh

Anal yte

l l B

47Ti

Cr

Mn

60Ni

6 3 c u

71Ga

'OZr

138Ba

I3'La

l4OCe

Semiquantitative Scanning mode

Peak jumping

2.2 0.2 4.5 10 .6 4.8 f0 .3

1.3f0.3

0.15 f O l

2.6

_+

0.2 1.3f0.15 1.0 .07

1.1 fO.1 0.7 .15 0.25 .09

1.5f0 .1 0.7 .05 1.1 f0 .04

0.05 .02


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1067

Table

6 Determination of the leachable and the non-leachable impurities in the A1,0, samples AKP-20 and AKP-30 by ICP-MS when leaching

with

2

(v/v) HN03. Figures in parentheses are the standard deviations from four replicate analyses. The results given for the alternative

methods are from acid decomposition of the sample without applying leaching with

2

HNO, (v/v)

Concentration/pg g-

'

Analyte

B

Na

Mg

Ca

Ti

V

Cr

Mn

Fe

c o

Ni

c u

Zn

Ga

Zr

Ba

La

Ce

A K P - 2 0 -

A K P - 3 0 -

B

Na

Mg

Ca

Ti

V

Cr

Mn

Fe

c o

Ni

c u

Zn

Ga

Zr

Ba

La

Ce

Leachable

2.8 (0.05)

2.8 (0.09)

0.98 (0.007)

0.07 (0.001)

0.2 (0.003)

0.15 (0.004)

0.026 (0.0003)

1.0

(0.1)

0.002 (0.00005)

0.1 (0.002)

0.55

(0.005)

0.33 (0.01)

0.006

(0.0003)

0.015 (0.0003)

0.046 (0.003)

0.037 (0.0005)

1.1 (0.02)

0.1 (0.002)

0.82 (0.02)

1.8 (0.04)

1.2 (0.3)

1.02 (0.02)

0.1 (0.001)

0.1 (0.002)

0.09 (0.002)

0.017 (0.0005)

0.8

(0.1)

0.002 (0.0003)

0.07

(0.001)

0.62 (0.003)

0.33 (0.002)

0.01 (0.0005)

0.015 (0.0003)

0.22 (0.004)

0.29 (0.005)

0.11 (0.002)

Non-leachable

6.5

analysis of aluminium oxide and silicon carbide ceramic materials

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